Compositions stabilized by dioxopiperazinyl derivatives

ABSTRACT

Polyoxymethylene, blends of polycarbonate with acrylonitrile-butadiene-styrene terpolymer, and coatings based on a functional acrylate resin and a crosslinking agent, which are stabilized by addition of a compound of the formula I  
                 
 
     wherein s is from the range 1 to 8;  
     R 1 , R 2 , R 3  and R 4 , independently of each other, are C 1 -C 4 alkyl, or R 1  and R 2  or R 3  and R 4 , together with the carbon atom to which they are bound, form a cyclopentyl or cyclohexyl ring; R 5  is hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH 2 CN; C 1 -C 18 alkoxy; C 5 -C 12 cycloalkoxy; C 3 -C 8 alkenyl; C 3 -C 8 alkynyl; C 7 -C 12 phenylalkyl; C 7 -C 15 phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; C 7 -C 15 phenylalkoxy; C 7 -C 15 phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R 5  is C 1 -C 8 alkanoyl; C 3 -C 5 alkenoyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group -CH 2 CH(OH)—G, in which G is hydrogen, methyl or phenyl; and A is as described in claim 1, show a good resistance against harmful effects of light, oxygen and heat.

[0001] The invention relates to compositions based on polyoxymethylene,blends of polycarbonate with acrylonitrile-butadiene-styrene terpolymer,or functional acrylate resin and crosslinking agent, which arestabilized by addition of a compound of the class of3,3,5,5-tetraalkyl-piperazin-2,6-dione, new compounds of this class, theuse of the novel compounds as stabilizers for organic material againstharmful effects of light, oxygen and/or heat, and organic materialstabilized correspondingly.

[0002] Structure and numbering of of3,3,5,5-tetraalkyl-piperazin-2,6-dione is as shown in the formula:

[0003] with R being alkyl.

[0004] Preparation of some of the above compounds, specific derivativesthereof, and use of these compounds as stabilizers e.g. forpolyethylene, polypropylene, nylon or ABS is shown by T. Yoshioka etal., Bull. Chem. Soc. Jap. 45,1855-1860 (1972); Luston and Vass,Makromol. Chem., Macromol. Symp. (1989), 27; and in the documents U.S.Pat. No. 4,413,096; C.A.99:141068; C.A. 96:104191; U.S. Pat. Nos.3,969,316; 3,936,456; 3,928,357; 3,928,330; 3,920,659; 3,919,234.

[0005] It has now been found, that certain compounds of the3,3,5,5-tetraalkyl-piperazin-2,6-dione class are especially wellsuitable as stabilizers for polyoxymethylene, blends of polycarbonatewith acrylonitrile-butadiene-styrene terpolymer, or coatings based on afunctional acrylate resin and a crosslinking agent.

[0006] The invention therefore pertains to a composition comprising

[0007] (A) a synthetic organic polymer selected from the groupconsisting of polyoxymethylene, a blend of polycarbonate withacrylonitrile-butadiene-styrene terpolymer, and a coating system basedon a functional acrylate resin and a crosslinking agent, and

[0008] (B) as stabilizer a compound of the formula I or II

[0009] wherein p is from the range 1 to 10;

[0010] s is from the range 1 to 8;

[0011] when s is 1,

[0012] A is C₁-C₁₈alkyl; C₂-C₁₈alkyl which is substituted by NH₂,hydroxy, halogen and/or OR₁₀ or interrupted by —O—, —NH— and/or —NR₁₀—;or A is C₁-C₁₈alkyl substituted by —COOR₁₁ or phenyl;

[0013] when s is 2,

[0014] A is C₂-C₁₀alkylene; C₄-C₁₂alkenylene; C₃-C₁₅alkylene substitutedby one or more OH and/or interrupted by one or more oxygen, phenylene,C₁-C₄alkylphenylene, —COO—, —CONH—,

[0015] when s is 3,

[0016] A is C₃-C₁₀alkantriyl; C₃-C₁₂alkantriyl substituted by OH and/orinterrupted by oxygen, —NH— or —NR₁₀—; or one of the groups of theformulae (IIa)-(IIId)

[0017] when s is 4,

[0018] A is C₄-C₁₀alkantetryl; C₄-C₁₂alkantetryl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (IVa)-(IVd)

[0019] when s is 5,

[0020] A is C₅-C₁₀alkanepentayl; C₅-C₁₂alkanepentayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (Va)-(Vc)

[0021] when s is 6,

[0022] A is C₆-C₁₀alkanehexayl; C₆-C₁₂alkanehexayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIa)-(VIf)

[0023] when s is 7,

[0024] A is C₇-C₁₀alkaneheptayl; C₇-C₁₂alkaneheptayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIIa)-(VIId)

[0025] when s is 8,

[0026] A is C₈-C₁₀alkaneoctayl; C₈-C₁₂alkaneoctayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIIIa)-(VIIIb)

[0027] the index i is zero or 1;

[0028] R₁, R₂, R₃ and R₄, independently of each other, are C₁-C₄alkyl,or R₁ and R₂ or R₃ and R₄, together with the carbon atom to which theyare bound, form a cyclopentyl or cyclohexyl ring;

[0029] R₅ is hydrogen; C₁-C₁₈alkyl; oxyl; OH; CH₂CN; C₁-C₁₈alkoxy;C₅-C₁₂cycloalkoxy; C₃-C₈alkenyl; C₃-C₈alkynyl; C₇-C₁₂phenylalkyl;C₇-C₁₅phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3radicals selected from C₁-C₄alkyl and C₁-C₄alkoxy; C₇-C₁₅phenylalkoxy;C₇-C₁₅phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3radicals selected from C₁-C₄alkyl and C₁-C₄alkoxy; or R₅ isC₁-C₈alkanoyl; C₃-C₅alkenoyl; C₁-C₁₈alkanoyloxy; glycidyl; or a group—CH₂CH(OH)—G, in which G is hydrogen, methyl or phenyl;

[0030] R₈ and R₉, and R₂₈, R₂₉, R₃₀, R₃₁, R₃₂ and R₃₃, independently ofeach other, are C₁-C₄alkylene;

[0031] R₁₀ is C₁-C₈alkyl, C₁-C₈alkanoyl, C₅-C₁₂cycloalkyl,C₇-C₁₅phenylalkyl which is unsubstituted or substituted on the phenylring by a radical selected from C₁-C₄alkyl and C₁-C₄alkoxy; or R₁₀ isC₁-C₈alkyl or C₁-C₈alkanoyl substituted by OH, C₁-C₁₂alkoxy and/or aresidue benzophenonyl or benzophenonyloxy, wherein one or both phenylrings of the benzophenone moiety are unsubstituted or substituted by OH,halogen, C₁-C₄alkyl and/or C₁-C₁₈alkoxy;

[0032] R₁₁ is C₁-C₁₈alkyl; C₂-C₁₈alkyl which is substituted by NH₂,NHR₁₀, N(R₁₀)₂, nitro, hydroxy and/or C₁-C₁₈alkoxy; C₃-C₁₈alkenyl;C₅-C₁₂cycloalkyl; C₅-C₁₂cycloalkyl which is substituted by C₁-C₄alkyland/or interrupted by —O—;

[0033] R₁₂, R₁₃ and R₁₄, independently of each other, areC₂-C₁₀alkylene; C₃-C₁₂alkylene substituted by OH and/or interrupted byoxygen, phenylene, C₁-C₄alkylphenylene, —NH— or —NR₁₀—;C₄-C₁₂alkenylene;

[0034] R₁₅ and R′_(15,) independently of each other, are isC₂-C₁₀alkylene; C₃-C₁₂alkylene substituted by OH and/or interrupted byoxygen, phenylene, C₁-C₄alkylphenylene, —NH— or —NR₁₀—;

[0035] R₁₆ is C₃-C₁₀alkantriyl; C₃-C₁₂alkantriyl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—;

[0036] R₁₇ is C₄-C₁₀alkantetryl; C₄-C₁₂alkantetryl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—;

[0037] R₁₈ is C₅-C₁₀alkanepentayl; C₅-C₁₂alkanepentayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—;

[0038] R₁₉ is C₆-C₁₀alkanehexayl; C₆-C₁₂alkanehexayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—;

[0039] X is —O—, —NH— or —N(R₁₀)—;

[0040] X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈, independently of each other,are —O— or —NH—;

[0041] Y is —O— or a residue of the formula

[0042] Z stands for halogen, NH₂, NHR₁₀, N(R₁₀)₂ or C₁-C₄alkoxy;

[0043] Z₁ has one of the meanings given for Z or is —X—R′₁₅—XH and

[0044] Z₂ is H or a residue of the formula

[0045] Where one compound carries more than one group denoted with thesame symbol, these groups may be the same or different within theirdefined meanings.

[0046] Alkylene, cycloalkylene or alkenylene residues may be bonded ondifferent carbon atoms or on the same carbon atom thus embracingalkylidene, cycloalkylidene and alkenylidene, respectively.

[0047] All residues, where appropriate, may be straight chain orbranched unless otherwise indicated. Hetero atoms are non-carbon atoms,for instance N, O, S or P atoms. Alkyl or alkylene interrupted by heterogroups such as oxygen or cycloalkylene may be interrupted by one or moreof these groups as long as no linkages of the type O—O, O—N etc. occur.

[0048] The index s is the valency of A; for example, A as alkyl is amonovalent, A as alkylene a divalent, A as alkanetriyl a trivalent, A asalkanetetryl a tetravalent, A as alkanepentayl a pentavalent, A asalkanehexayl a hexavalent, A as alkaneheptayl a heptavalent, and A asalkaneoctayl an octovalent saturated hydrocarbon residue. A residuewhich is interrupted is interrupted in a carbon-carbon single bond. Aresidue which is interrupted and/or substituted may be a residueinterrupted in one or more carbon-carbon single bonds by one or moredivalent interrupting groups, a residue substituted by one or moremonovalent substituents, or a residue which is both interrupted in oneor more carbon-carbon single bonds by one or more divalent interruptinggroups and substituted by one or more monovalent substituents.

[0049] Thus, examples for A as C₃-C₁₅alkylene substituted by one or moreOH and/or interrupted by oxygen, phenylene, C₁-C₄alkylphenylene, —COO—,—CONH—, —NH— or —NR₁₀— include groups of the formulae CH₂CH(OH)CH₂,CH₂—C(CH₂OH)₂—CH₂, (CH₂)₂—N(CHO)—(CH₂)₂, (CH₂)₂—NH—(CH₂)₂,(CH₂)₂—O—(CH₂)₂, (CH₂)₂—O—(CH₂)₂—O—(CH₂)₂,CH₂—CO—O—(CH₂)₂—O—(CH₂)₂—O—CO—CH₂, CH₂—CO—O—(CH₂)₆—O—CO—CH₂,CH₂—CO—O—(CH₂)₂—O—CO—CH₂.

[0050] Halogen is preferably chloro or bromo, especially chloro.

[0051] C₆-C₁₂aryl is preferably phenyl or naphthyl, especially phenyl.

[0052] The compounds of the invention can be pure or mixtures ofcompounds.

[0053] R₁ R₂, R₃, R₄, R₅, R₁₀ as alkyl are, within the definitionsgiven, for example methyl, ethyl, propyl such as n- or isopropyl, butylsuch as n-, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl or octadecyl.

[0054] R₈, R₉, R₁₂, R₁₃, R₁₄, R₁₅, R′₁₅ and R₂₈-R₃₃ as alkylene are,within the definitions given, for example methylene, 1,2-ethylene,1,1-ethylene, 1,3-propylene, 1,2-propylene, 1,1-propylene,2,2-propylene, 1,4-butylene, 1,3-butylene, 1,2-butylene, 1,1-butylene,2,2-butylene, 2,3-butylene, or -C₅H,O—, —C₆H₁₂—, C₇H₁₄, —C₈H₁₆—,—C₉H₁₈—, —C₁₀H₂₀—, —C₁₁H₂₂—, —C₁₂H₂₄—, —C₁₃H₂₆—, —C₁₄H₂₈-, —C₁₅H₃₀—,—C₁₆H₃₂—, —C₁₇H₃₄—, —C₁₈H₃₆—.

[0055] R₈, R₉ and R₂₈-R₃₃ are especially preferred as methylene.

[0056] In R₅, R₁₀, R₁₁ as C₅-C₁₂cycloalkyl or cycloalkoxy, thecycloalkyl part is, for example, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl.C₅-C₁₂-Cycloalkenyl includes cyclopentenyl, cyclohexenyl, cycloheptenyl,cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl,cyclododecenyl.

[0057] C₁-C₄alkyl or akloxy substituted cycloalkyl or phenyl (containingmainly 1-3, e.g. 1 or 2 alkyl groups) include inter alia 2- or4-methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl,t-butylcyclohexyl, methylphenyl, methoxyphenyl, dimethylphenyl.

[0058] Phenylalkyl or phenylalkoxy are alkyl or alkoxy each of which issubstituted by phenyl. R₅, R₁₀ as phenylalkyl or phenylalkoxy are,within the definitions given, for example benzyl, benzyloxy,a-methylbenzyl, a-methylbenzyloxy, cumyl, cumyloxy.

[0059] R₅ and R₁₀ as alkanoyl are, for example, formyl, acetyl,propionyl, butyryl, pentanoyl, octanoyl; R₅ as alkanoyl is preferred asC₂-C₈alkanoyl, especially acetyl.

[0060] Residues alkenoyl, such as in the definition of R₅, are mostpreferably acryloyl or methacryloyl.

[0061] Residues alkenyl, such as in the definition of R₅, are mostpreferably allyl.

[0062] X is preferably NH; X₁-X₆ are most preferably O; Z is mostpreferred as N(R₁₀)₂; i is most preferred as zero.

[0063] The index p is preferably from the range 2-6.

[0064] A preferred blend of polycarbonate withacrylonitrile-butadiene-styrene terpolymer (component (A) of the abovecomposition) is a blend of 10 to 90 parts by weight of polycarbonatewith 90 to 10 parts by weight of acrylonitrile-butadiene-styreneterpolymer.

[0065] Polycarbonates contained in these blends are to be understood asbeing especially those polymers the constitutional repeating unit ofwhich corresponds to the formula,

[0066] wherein W is a divalent phenolic radical. Examples of W are giveninter alia in U.S. Pat. No. 4,960,863 and DE-A-3922496. W can bederived, for example, from hydroquinone, resorcinol,dihydroxybiphenylene or bisphenols in the broadest sense of the term,such as bis(hydroxyphenyl)alkanes, cycloalkanes, sulfides, ethers,ketones, sulfones, sulfoxides,α,α′-bis(hydroxyphenyl)diisopropylbenzenes, for example the compounds2,2-bis(4-hydroxyphenyl)propane,2,2-bis(3,5-dimethyl-4-hydroxy-phenyl)propane,2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)cyclohexane, or from the bisphenols of the

[0067] The composition of the invention preferably contains as furthercomponent (C) a UV absorber from the class of the benzotriazoles,o-hydroxyphenyl-s-triazines and/or benzophenones, examples of which arelisted below.

[0068] Preferred is composition, wherein in the compound of formula I(component B) s is from the range 2 to 6;

[0069] when s is 2

[0070] A is C₂-C₁₀alkylene; C₃-C₁₂alkylene substituted by OH and/orinterrupted by oxygen, —NH— or —NR₁₀—; or a group of the formula—R₈—COO—R₁₂—OCO—R₉— (IIa);

[0071] when s is 3,

[0072] A is a group of the formula (IIIa)

[0073] when s is 4,

[0074] A is one of the groups of the formulae (IVa) or (IVd)

[0075] when s is 5,

[0076] A is a group of the formula (Va)

[0077] when s is 6,

[0078] A is one of the groups of the formulae (VIb)-(VIf)

[0079] the index is zero is 1;

[0080] R₁, R₂, R₃ and R₄, independently of each other, are methyl;

[0081] R₅ is hydrogen; C₁-C₁₈alkyl; oxyl; OH; C₁-C₁₈alkoxy;C₅-C₁₂cycloalkoxy; C₃-C₈alkenyl; or R₅ is

[0082] C₁-C₈alkanoyl; C₃-C₅alkenoyl; C₁-C₁₈alkanoyloxy; glycidyl; or agroup —CH₂CH(OH)—G, in which G is hydrogen, methyl or phenyl;

[0083] R₈ and R₉, and R₂₈, R₂₉, R₃₀, R₃₁ , R₃₂ and R₃₃, independently ofeach other, are methylene;

[0084] R₁₀ is C₁-C₈alkyl, C₁-C₈alkanoyl, C₅-C₁₂C₁₂cycloalkyl;

[0085] R₁₂ is C₂-C₁₀alkylene; or C₃-C₁₂alkylene interrupted by oxygen,—NH— or —NR₁₀—;

[0086] R₁₅ and R′₁₅, independently of each other, are is C₂-C₁₀alkylene;

[0087] R₁₇ is C₄-C₁₀alkantetryl;

[0088] R₁₈ is C₅-C₁₀alkanepentayl;

[0089] X is —O—, —NH— or —N(R₁₀)—;

[0090] X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈, independently of each other,are —O— or —NH—; and

[0091] Z stands for NHR₁₀, N(R₁₀)₂ or C₁-C₄alkoxy.

[0092] Many compounds of the above component B are novel. The inventiontherefore also relates to a compound of the formula (I′) or (II)

[0093] wherein p is from the range 1-10;

[0094] s is from the range 1 to 8, preferably 2 to 8;

[0095] R₁, R₂, R₃ and R₄, independently of each other, are C₁-C₄alkyl;

[0096] R₅ is hydrogen; C₁-C₁₈alkyl; oxyl; OH; CH₂CN; C₁-C₁₈alkoxy;C₅-C₁₂cycloalkoxy; C₃-C₈alkenyl; C₃-C₈alkynyl; C₇-C₁₂phenylalkyl;C₇-C₁₅phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3radicals selected from C₁-C₄alkyl and C₁-C₄alkoxy; C₇-C₁₅phenylalkoxy;C₇-C₁₅phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3radicals selected from C₁-C₄alkyl and C₁-C₄alkoxy; or R₅ isC₁-C₈alkanoyl; C₃-C₅alkenoyl; C₁-C₁₈alkanoyloxy; glycidyl; or a group—CH₂CH(OH)—G, in which G is hydrogen, methyl or phenyl;

[0097] when s is 1, A is C₂-C₁₈alkylene substituted by OR₃₀, wherein R₃₀is C₁-C₈alkyl or C₁-C₈alkanoyl substituted by a residue benzophenonyl orbenzophenonyloxy, wherein one or both phenyl rings of the benzophenonemoiety are unsubstituted or substituted by OH, halogen, C₁-C₄alkyland/or C₁-C₁₈alkoxy;

[0098] when s is 2

[0099] A is C₃-C₁₅alkylene substituted by one or more OH and/orinterrupted by one or more oxygen, phenylene, C₁-C₄alkylphenylene,—COO—, —CONH—,

[0100] —NH— and/or —NR₁₀—; or A is C₄-C₁₂alkenylene;

[0101] and when R₅ is not hydrogen, A also embraces C₂-C₁₀alkylene;C₂-C₁₀alkylene interrupted by phenylene or C₁-C₄alkylphenylene;

[0102] when s is 3,

[0103] A is C₃-C₁₀alkantriyl; C₃-C₁₂alkantriyl substituted by OH and/orinterrupted by oxygen, —NH— or —NR₁₀—; or one of the groups of theformulae (IIIa)-(IIId)

[0104] when s is 4,

[0105] A is C₄-C₁₀alkantetryl; C₄-C₁₂alkantetryl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (IVa)-(IVd)

[0106] when s is 5,

[0107] A is C₅-C₁₀alkanepentayl; C₅-C₁₂alkanepentayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (Va)-(Vc)

[0108] when s is 6,

[0109] A is C₆-C₁₀alkanehexayl; C₆-C₁₂alkanehexayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIa)-(VIf)

[0110] when s is 7,

[0111] A is C₇-C₁₀alkaneheptayl; C₇-C₁₂alkaneheptayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIIa)-(VIId)

[0112] when s is 8,

[0113] A is C₈-C₁₀alkaneoctayl; C₈-C₁₂alkaneoctayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIIIa)-(VIIIb)

[0114] the index i is zero or 1;

[0115] R₈ and R₉, and R₂₈, R₂₉, R₃₀, R₃₁, R₃₂ and R₃₃, independently ofeach other, are methylene, and when R₅ is not hydrogen, additionallyembrace ethylene;

[0116] R₁₀ is C₁-C₈alkyl, C₁-C₈alkanoyl, C₅-C₁₂cycloalkyl,C₇-C₁₅phenylalkyl which is unsubstituted or substituted on the phenylring by a radical selected from C₁-C₄alkyl and C₁-C₄alkoxy;

[0117] R₁₂, R₁₃ and R₁₄, independently of each other, areC₂-C₁₀alkylene; C₃-C₁₂alkylene substituted by OH and/or interrupted byoxygen, phenylene, C₁-C₄alkylphenylene, —NH— or —NR₁₀—;C₄-C₁₂alkenylene;

[0118] R₁₅ and R′₁₅, independently of each other, are is C₂-C₁₀alkylene;C₃-C₁₂alkylene substituted by OH and/or interrupted by oxygen,phenylene, C₁-C₄alkylphenylene, —NH— or —NR₁₀—;

[0119] R₁ is C₃-C₁₀alkantriyl; C₃-C₁₂alkantriyl substituted by OH and/orinterrupted by oxygen, —NH— or —NR₁₀—;

[0120] R₁₇ is C₄-C₁₀alkantetryl; C₄-C₁₂alkantetryl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—;

[0121] R₁₈ is C₅-C₁₀alkanepentayl; C₅-C₁₂alkanepentayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—;

[0122] R₁₉ is C₆-C₁₀alkanehexayl; C₆-C₁₂alkanehexayl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—;

[0123] X is —O—, —NH— or —N(R₁₀)—;

[0124] X₁, X₂, X₃, X₄, X₅, X₆, independently of each other, are —O— or—NH—;

[0125] Y is —O— or a residue of the formula

[0126] Z stands for halogen, NH₂, NHR₁₀, N(R₁₀)₂ or C₁-C₄alkoxy;

[0127] Z₁ has one of the meanings given for Z or is —X—R′₁₅—XH and

[0128] Z₂ is H or a residue of the formula

[0129] Preferred meanings in the formula (I′) include those given abovefor formula (I), where appropriate.

[0130] Also preferred is a compound of the formula (I′) or (II) whereinp is from the range 2-6, s is from the range 2 to 8;

[0131] R₁, R₂, R₃ and R₄, independently of each other, are methyl orethyl;

[0132] R₅ is hydrogen; C₁-C₁₈alkyl; oxyl; OH; CH₂CN; C₁-C₁₈alkoxy;C₅-C₁₂cycloalkoxy; C₃-C₈alkenyl; C₇-C₁₂phenylalkyl; C₇-C₁₅phenylalkoxy;or R₅ is C₁-C₈alkanoyl; C₃-C₅alkenoyl; C₁-C₁₈alkanoyloxy; glycidyl; or agroup —CH₂CH(OH)—G, in which G is hydrogen, methyl or phenyl;

[0133] when s is 2

[0134] A is C₃-C₁₂alkylene substituted by OH and/or interrupted byoxygen, —NH— or —NR₁₀—;

[0135] C₄-C₁₂alkenylene; or one of the groups of the formulae(IIa)-(IIe)

[0136] and when R₅ is not hydrogen, A also embraces C₂-C₁₀alkylene;C₂-C₁₀alkylene interrupted by phenylene or C₁-C₄alkylphenylene;

[0137] when s is 3,

[0138] A is C₃-C₁₀alkantriyl; or one of the groups of the formulae(IIIa)-(IIId)

[0139] when s is 4,

[0140] A is C₄-C₁₀alkantetryl; or one of the groups of the formulae(IVa)-(IVd)

[0141] when =is 5,

[0142] A is C₅-C₁₀alkanepentayl; or a group of the formula (Va)

[0143] when s is 6,

[0144] A is C₆-C₁₀alkanehexayl; or one of the groups of the formulae(VIb)-(VIf)

[0145] when s is 7,

[0146] A is C₇-C₁₀alkaneheptayl;

[0147] when s is 8,

[0148] A is C₈-C₁₀alkaneoctayl; or one of the groups of the formulae(VIIIa)-(VIIIb); the index i is zero or 1;

[0149] R₈ and R₉, and R₂₈, R₂₉, R₃₀, R₃₁, R₃₂ and R₃₃, independently ofeach other, are methylene;

[0150] R₁₀ is C₁-C₈alkyl, C₁-C₈alkanoyl, C₅-C₁₂cycloalkyl,C₇-C₁₅phenylalkyl;

[0151] R₁₂, R₁₃ and R₁₄, independently of each other, areC₂-C₁₀alkylene; C₃-C₁₂alkylene substituted by OH and/or interrupted byoxygen, —NH— or —NR₁₀—; C₄-C₁₂alkenylene;

[0152] R₁₅ and R′₁₅, independently of each other, are is C₂-C₁₀alkylene;C₃-C₁₂alkylene substituted by OH and/or interrupted by oxygen,phenylene, C₁-C₄alkylphenylene, —NH— or —NR₁₀—;

[0153] R₁₆ is C₃-C₁₀alkantriyl;

[0154] R₁₇ is C₄-C₁₀alkantetryl;

[0155] R₁₈ is C₅-C₁₀alkanepentayl;

[0156] X is —O—, —NH— or —N(R₁₀)—;

[0157] X₁, X₂, X₃, X₄, X₅, independently of each other, are —o— or —NH—;and

[0158] Z stands for halogen, NH₂, NHR₁₀, N(R₁₀)₂ or C₁-C₄alkoxy.

[0159] Especially preferred is a compound of the formula (I′) wherein sis from the range 2 to 6;

[0160] R₁, R₂, R₃ and R₄, independently of each other, are methyl orethyl;

[0161] R₅ is hydrogen; C₁-C₁₈alkyl; oxyl; OH; CH₂CN; C₁-C₁₈alkoxy;C₅-C₁₂cycloalkoxy; C₃-C₈alkenyl; C₇-C₁₂phenylalkyl; C₇-C₁₅phenylalkoxy;or R₅ is C₁-C₈alkanoyl; C₃-C₅alkenoyl; C₁-C₁₈alkanoyloxy; glycidyl; or agroup —CH₂CH(OH)—G, in which G is hydrogen, methyl or phenyl;

[0162] when s is 2

[0163] A is C₃-C₁₂alkylene substituted by OH and/or interrupted byoxygen, —NH— or —NR₁₀—;

[0164] C₄-C₁₂alkenylene; or a group of the formula (IIa)

—R₈—COO—R₁₂—OCO—R₉—;   (IIa)

[0165] and when R₅ is not hydrogen, A also embraces C₂-C₁₀alkylene;

[0166] when s is 3,

[0167] A is C₃-C₁₀alkantriyl; or one of the groups of the formulae(IIIa), (IIIb) or (IIId);

[0168] when s is 4,

[0169] A is C₄-C₁₀alkantetryl; or one of the groups of the formulae(IVa), (IVb) or (IVd);

[0170] when s is 5,

[0171] A is C₅-C₁₀alkanepentayl;

[0172] when s is 6,

[0173] A is one of the groups of the formulae (VIb)-(VIf);

[0174] the index i is zero or 1;

[0175] R₈ and R₉, and R₂₈, R₂₉, R₃₀, R₃₁, R₃₂ and R₃₃, independently ofeach other, are methylene;

[0176] R₁₀ is C₁-C₈alkyl, C₁-C₈alkanoyl, C₅-C₁₂cycloalkyl;

[0177] R₁₂ is C₂-C₁₀alkylene; C₃-C₁₂alkylene substituted by OH and/orinterrupted by oxygen, —NH— or —NR₁₀—;

[0178] R₁₅ and R′₁₅, independently of each other, are is C₂-C₁₀alkylene;

[0179] R₁₆ is C₃-C₁₀alkantriyl;

[0180] R₁₇ is C₄-C₁₀alkantetryl;

[0181] X is —O—, —NH— or —N(R₁₀)—;

[0182] X₁, X₂, X₃, X₄, independently of each other, are —O— or —NH—; and

[0183] Z stands for NHR₁₀ or N(R₁₀)₂.

[0184] Most preferred is a compound of the formula (I′) wherein s is 2,3, 4 or 6;

[0185] R₁, R₂, R₃ and R₄ are methyl;

[0186] R₅ is hydrogen; C₁-C₈alkyl; C₁-C₁₈alkoxy; cyclohexyloxy; allyl;benzyl; acetyl; C₃-C₄alkenoyl; glycidyl;

[0187] when s is 2

[0188] A is C₃-C₁₀alkylene substituted by OH or interrupted by oxygen,—NH— or —NR₁₀—; or a group of the formula —R₈—COO—R₁₂—OCO—R₉— (IIa); andwhen R₅ is not hydrogen, A also embraces C₂-C₁₀alkylene;

[0189] when s is 3, A is a group of the formula (IIIa);

[0190] when s is 4, A is a group of the formula (IVa) or (IVd);

[0191] when s is 6, A is a groups of the formula (VIe); the index i iszero;

[0192] R₈ and R₉, and R₂₈, R₂₉, R₃₀, R₃₁, R₃₂ and R₃₃ are methylene;

[0193] R₁₀ is C₁-C₈alkyl, formyl, acetyl, or cyclohexyl;

[0194] R₁₂ is C₂-C₁₀alkylene; or C₃-C₁₀alkylene interrupted by oxygen;

[0195] R₁₅ and R′₁₅, independently of each other, are is C₂-C₁₀alkylene;

[0196] R₁₇ is C₄-C₁₀alkantetryl;

[0197] X is —NH—;

[0198] X₁, X₂, X₃, X₄ are —O—; and

[0199] Z stands for N(R₁₀)₂.

[0200] The preparation of compounds of the formula I or I′ can startfrom the compound 3,3,5,5-tetraalkyl-piperazin-2,6-dione and can followor be carried out in analogy to methods described in the documents citedon page 1 or standard procedures described in textbooks of organicchemistry; examples for such methods are alkylation,(trans)esterification or etherification, substitution etc.

[0201] Compounds thus obtained may be further derivatized by applyingsuitable synthetic methods known in the art, e.g. in analogy to methodsdescribed in EP-A-375612, U.S. Pat. Nos. 5,204,473, 5,004,770, andKurumada et al., J. Polym. Sci., Poly. Chem. Ed. 23,1477 (1985), as wellas U.S. Pat. No. 5,449,776, example 8, and publications cited therein,for the modification of piperidine derivatives.

[0202] The novel compounds of present invention can be employed withadvantage for stabilizing organic material against the damaging effectof light, oxygen and/or heat. They are notable for high substratecompatibility and good persistence in the substrate.

[0203] Examples of materials to be stabilized in accordance with theinvention are:

[0204] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), highdensity and high molecular weight polyethylene (HDPE-HMW), high densityand ultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

[0205] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0206] a) radical polymerisation (normally under high pressure and atelevated temperature).

[0207] b) catalytic polymerisation using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerisation medium. The catalysts can be used by themselves inthe polymerisation or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0208] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0209] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0210] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

[0211] 5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).

[0212] 6. Copolymers of styrene or a-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene,styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

[0213] 7. Graft copolymers of styrene or x-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

[0214] 8. Halogen-containing polymers such as polychloroprene,chlorinated rubbers, chlorinated and brominated copolymer ofisobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinatedpolyethylene, copolymers of ethylene and chlorinated ethylene,epichlorohydrin homo- and copolymers, especially polymers ofhalogen-containing vinyl compounds, for example polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, aswell as copolymers thereof such as vinyl chloride/vinylidene chloride,vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetatecopolymers.

[0215] 9. Polymers derived from o,p-unsaturated acids and derivativesthereof such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylonitriles, impact-modifiedwith butyl acrylate.

[0216] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

[0217] 11. Polymers derived from unsaturated alcohols and amines or theacyl derivatives or acetals thereof, for example polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

[0218] 12. Homopolymers and copolymers of cyclic ethers such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0219] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain ethylene oxide as a comonomer;polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0220] 14. Polyphenylene oxides and sulfides, and mixtures ofpolyphenylene oxides with styrene polymers or polyamides.

[0221] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0222] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, for example polyamide 4, polyamide 6, polyamide6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromaticpolyamides starting from m-xylene diamine and adipic acid; polyamidesprepared from hexamethylenediamine and isophthalic or/and terephthalicacid and with or without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

[0223] 17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

[0224] 18. Polyesters derived from dicarboxylic acids and diols and/orfrom hydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

[0225] 19. Polycarbonates and polyester carbonates.

[0226] 20. Polysulfones, polyether sulfones and polyether ketones.

[0227] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0228] 22. Drying and non-drying alkyd resins.

[0229] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0230] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

[0231] 25. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, isocyanates,isocyanurates, polyisocyanates or epoxy resins.

[0232] 26. Crosslinked epoxy resins derived from aliphatic,cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g.products of diglycidyl ethers of bisphenol A and bisphenol F, which arecrosslinked with customary hardeners such as anhydrides or amines, withor without accelerators.

[0233] 27. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, for examplecellulose acetates, cellulose propionates and cellulose butyrates, orthe cellulose ethers such as methyl cellulose; as well as rosins andtheir derivatives.

[0234] 28. Blends of the aforementioned polymers (polyblends), forexample PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PAIPPO, PBT/PC/ABSor PBT/PET/PC.

[0235] The invention therefore also provides compositions comprising

[0236] A) an organic material which is sensitive to oxidative, thermaland/or actinic degradation, and

[0237] B) at least one compound of the formula I′, and provides for theuse of compounds of the formula I′ for stabilizing organic materialagainst oxidative, thermal or actinic degradation.

[0238] Effects of degradation inter alia may be discoloration, molecularbreakdown or buildup. Thus, the invention likewise embraces a method ofstabilizing organic material against thermal, oxidative and/or actinicbreakdown/buildup, which comprises applying or adding at least onecompound of the formula I′ to this material.

[0239] In general, the compounds of the formula I or I′ are added to thematerial to be stabilized in amounts of from 0.1 to 10%, preferably from0.01 to 5%, in particular from 0.01 to 2% (based on the material to bestabilized). Particular preference is given to the use of the novelcompounds in amounts of from 0.05 to 1.5%, especially from 0.1 to 0.5%.

[0240] In addition to the compounds of the formula I or I′, the novelcompositions may as additional component C comprise one or moreconventional additives such as, for example, those indicated below.

[0241] 1. Antioxidants

[0242] 1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethyl-phenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-di-methyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

[0243] 1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioc-tylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

[0244] 1.3. Hydroquinones and alkylated hydroguinones, for example2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0245] 1.4. TocoPherols, for example α-tocopherol, β-tocopherol,γ-tocopherol, δ-tocopherol and mixtures thereof (Vitamin E).

[0246] 1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

[0247] 1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0248] 1.7. O—, N— and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydi-benzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0249] 1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-te-tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0250] 1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame-thylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0251] 1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0252] 1.11. Benzvlphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0253] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0254] 1.13. Esters of β-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethyihexanediol,trimethylol-propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0255] 1.14. Esters ofβ-(5-tert-butyl-4-hvdroxy-3-methylnhenyl)propionic acid with mono- orpolyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol,octadecanol, 1,6-hexane-diol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0256] 1.15. Esters of β-(3,5-dicyclohexyl-4-hvdroxyyhenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)ox-amide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0257] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)ox-amide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0258] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).

[0259] 1.18. Ascorbic acid (vitamin C)

[0260] 1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclo-hexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxy-diphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylamino-phenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenyimethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyidiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dial-kylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

[0261] 2. UV absorbers and light stabilisers

[0262] 2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzo-triazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyi)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxy-carbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonyiethyl)phenylbenzotriazole,2,2′-methylene-bis-[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂ ₂ whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

[0263] 2.2. 2-Hydroxvbenzophenones, for example the 4-hydroxy,4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0264] 2.3. Esters of substituted and unsubstituted benzoic acids, asfor example 4-tertbutyl-phenyl salicylate, phenyl salicylate,octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

[0265] 2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate,isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate,methyl α-cyano-β-methyl-β-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0266] 2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetrame-thylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

[0267] 2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-pi-peridyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetrame-thylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane und epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

[0268] 2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

[0269] 2.8. 2-(2-Hvdroxyphenvl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-3,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1 ,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

[0270] 3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

[0271] 4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-bu-tylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite.

[0272] Especially preferred are the following phosphites:

[0273] Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168,Ciba-Geigy), tris(nonylphenyl) phosphite,

[0274] (G)

[0275] 5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhy-droxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0276] 6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhy-droxylamine derived from hydrogenated tallow amine.

[0277] 7. Thiosyner ists, for example, dilauryl thiodipropionate ordistearyl thiodipropionate.

[0278] 8. Peroxide scavengers, for example esters of P-thiodipropionicacid, for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(5-dodecylmercapto)propionate.

[0279] 9. Polvamide stabilisers, for example, copper salts incombination with iodides and/or phosphorus compounds and salts ofdivalent manganese.

[0280] 10. Basic co-stabilisers, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acidsfor example calcium stearate, zinc stearate, magnesium behenate,magnesium stearate, sodium ricinoleate and potassium palmitate, antimonypyrocatecholate or zink pyrocatecholate.

[0281] 11. Nucleating agents, for example, inorganic substances such astalcum, metal oxides such as titanium dioxide or magnesium oxide,phosphates, carbonates or sulfates of, preferably, alkaline earthmetals; organic compounds such as mono- or polycarboxylic acids and thesalts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate or sodium benzoate; polymericcompounds such as ionic copolymers (ionomers).

[0282] 12. Fillers and reinforcing agents, for example, calciumcarbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin,mica, barium sulfate, metal oxides and hydroxides, carbon black,graphite, wood flour and flours or fibers of other natural products,synthetic fibers.

[0283] 13. Other additives, for example, plasticisers, lubricants,emulsifiers, pigments, rheology additives, catalysts, flow-controlagents, optical brighteners, flameproofing agents, antistatic agents andblowing agents.

[0284] 14. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. Nos. 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643;DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0285] The conventional additives are judiciously employed in amounts of0.1-10% by weight, for example 0.2-5% by weight, based on the materialto be stabilized.

[0286] Costabilizers optionally to be added to the stabilizer mixture ofthe invention are preferably further light stabilizers, for instancethose of the 2-hydroxyphenyl-benztriazole, 2-hydroxyphenyl-triazine,benzophenone or oxalanilide classes, e.g. as described in EP-A-453396,EP-A-434608, U.S. Pat. No. 5,298,067, WO 94/18278, GB-A-2297091 and WO96/28431, and/or further hindered amines derived from2,2,6,6-tetraalkylpiperidine containing at least one group of theformula

[0287] in which G is hydrogen or methyl, especially hydrogen; examplesof tetraalkylpiperidine derivatives which can be used as costabilizerswith mixtures of the invention are given in EP-A-356 677, pages 3-17,sections a) to f). These sections of this EP-A are regarded as part ofthe present description.

[0288] Especially preferred as costabilizers are2-hydroxyphenyl-benztriazoles and/or 2-hydroxyphenyl-triazines.

[0289] Of particular interest is the use of compounds of the formula I′as stabilizers in synthetic organic polymers, especially thermoplasticpolymers, and corresponding compositions, in film forming binders forcoatings and in reprographic material.

[0290] The organic materials to be protected are preferably natural,semisynthetic or, preferably, synthetic organic materials. Particularpreference is given to synthetic organic polymers or mixtures of suchpolymers, especially thermoplastic polymers such as polyolefins,especially polyethylene and polypropylene (PP), and coatingcompositions. Of special importance are also polycarbonates and blendsthereof, for example the polymers listed above under items 19 and 28.

[0291] Incorporation into the materials can be effected, for example, bymixing in or applying the compounds of the formula I′ and, if desired,further additives by the methods which are customary in the art. Wherepolymers are involved, especially synthetic polymers, incorporation cantake place prior to or during the shaping operation, or by applying thedissolved or dispersed compound to the polymer, with or withoutsubsequent evaporation of the solvent. In the case of elastomers, thesecan also be stabilized as latices. A further possibility forincorporating the compounds of the formula I′ into polymers is to addthem before, during or directly after the polymerization of thecorresponding monomers or prior to crosslinking. In this context thecompound of the formula can be added as it is or else in encapsulatedform (for example in waxes, oils or polymers). In the case of additionprior to or during the polymerization, the compounds of the formula I′can also act as a regulator of the chain length of the polymers (chainterminator).

[0292] The compounds of the formula I or I′ can also be added in theform of a masterbatch containing said compound in a concentration, forexample, of from 2.5 to 25% by weight to the polymers that are to bestabilized.

[0293] The compounds of the formula I or I′ can judiciously beincorporated by the following methods:

[0294] as emulsion or dispersion (e.g. to latices or emulsion polymers),

[0295] as a dry mixture during the mixing in of additional components orpolymer mixtures,

[0296] by direct introduction into the processing apparatus (e.g.extruders, internal mixers, etc),

[0297] as solution or melt.

[0298] Novel polymer compositions can be employed in various formsand/or processed to give various products, for example as (to give)films, fibres, tapes, moulding compositions, profiles, or as binders forcoating materials, adhesives or putties.

[0299] Other materials to be stabilized according to the invention arerecording materials. By such materials are meant, for example, thosedescribed in Research Disclosure 1990, 31429 (pages 474-480) forphotographic reproduction and other reprographic techniques.

[0300] The novel recording materials comprise, for example, those forpressure-sensitive copying systems, microcapsule photocopier systems,heat-sensitive copier systems, photographic material and ink-jetprinting.

[0301] The novel photographic material can be a black and white or acolour photographic material; colour photographic material is preferred.Further details on the structure of colour photographic material, andthe components which can be employed in the novel material, can befound, inter alia, in U.S. Pat. No. 5,538,840, column 27, line 25, tocolumn 106, line 16, and in the publications cited therein; thesepassages of U.S. Pat. No. 5,538,840 are hereby incorporated byreference. Application of the novel stabilizers of the formula I′ isessentially as described for UV absorbers or hindered amine stabilizersin this reference. Further important components, especially couplers,are described in U.S. Pat. No. 5,578,437.

[0302] Likewise of particular interest is the use of the novel mixturescomprising compounds of the formula (I) as stabilizers for coatings, forexample for paints. The invention therefore also relates to thosecompositions whose component (A) is a film-forming binder for coatings.

[0303] The novel coating composition preferably comprises 0.01-10 partsby weight of (B), in particular 0.05-10 parts by weight of (B),especially 0.1-5 parts by weight of (B), per 100 parts by weight ofsolid binder (A).

[0304] Multilayer systems are possible here as well, where theconcentration of the novel stabilizer (component (B)) in the outer layercan be relatively high, for example from 1 to 15 parts by weight of (B),in particular 3-10 parts by weight of (B), per 100 parts by weight ofsolid binder (A).

[0305] The use of the compounds of the formula I or I′ in coatings isaccompanied by the additional advantage that it prevents delamination,i.e. the flaking-off of the coating from the substrate. This advantageis particularly important in the case of metallic substrates, includingmultilayer systems on metallic substrates.

[0306] The binder (component (A)) can in principle be any binder whichis customary in industry, for example those described in Ullmann'sEncyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.368-426, VCH, Weinheim 1991. In general, it is a film-forming binderbased on a thermoplastic or thermosetting resin, predominantly on athermosetting resin. Examples thereof are alkyd, acrylic, polyester,phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

[0307] Component (A) can be a cold-curable or hot-curable binder; theaddition of a curing catalyst may be advantageous. Suitable catalystswhich accelerate curing of the binder are described, for example, inUllmann's Encyclopedia of Industrial Chemistry, Vol. Al18, p.469, VCHVerlagsgesellschaft, Weinheim 1991.

[0308] Preference is given to coating compositions in which component(A) is a binder comprising a functional acrylate resin and acrosslinking agent.

[0309] Examples of coating compositions containing specific binders are:

[0310] 1. paints based on cold- or hot-crosslinkable alkyd, acrylate,polyester, epoxy or melamine resins or mixtures of such resins, ifdesired with addition of a curing catalyst;

[0311] 2. two-component polyurethane paints based on hydroxyl-containingacrylate, polyester or polyether resins and aliphatic or aromaticisocyanates, isocyanu rates or polyisocyanates;

[0312] 3. one-component polyurethane paints based on blockedisocyanates, isocyanurates or polyisocyanates which are deblocked duringbaking, if desired with addition of a melamine resin;

[0313] 4. one-component polyurethane paints based on atrisalkoxycarbonyltriazine crosslinker and a hydroxyl group containingresin such as acrylate, polyester or polyether resins;

[0314] 5. one-component polyurethane paints based on aliphatic oraromatic urethaneacrylates or polyurethaneacrylates having free aminogroups within the urethane structure and melamine resins or polyetherresins, if necessary with curing catalyst;

[0315] 6. two-component paints based on (poly)ketimines and aliphatic oraromatic isocyanates, isocyanurates or polyisocyanates;

[0316] 7. two-component paints based on (poly)ketimines and anunsaturated acrylate resin or a polyacetoacetate resin or amethacrylamidoglycolate methyl ester;

[0317] 8. two-component paints based on carboxyl- or amino-containingpolyacrylates and polyepoxides;

[0318] 9. two-component paints based on acrylate resins containinganhydride groups and on a polyhydroxy or polyamino component;

[0319] 10. two-component paints based on acrylate-containing anhydridesand polyepoxides;

[0320] 11. two-component paints based on (poly)oxazolines and acrylateresins containing anhydride groups, or unsaturated acrylate resins, oraliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

[0321] 12. two-component paints based on unsaturated polyacrylates andpolymalonates;

[0322] 13. thermoplastic polyacrylate paints based on thermoplasticacrylate resins or externally crosslinking acrylate resins incombination with etherified melamine resins;

[0323] 14. paint systems based on siloxane-modified or fluorine-modifiedacrylate resins;

[0324] 15. paint systems , especially for clearcoats, based on malonate-blocked isocyanates with melamine resins (e.g.hexamethoxymethylmelamine) as crosslinker (acid catalyzed);

[0325] 16. UV-curable systems based on oligomeric urethane acrylates, oroligomeric urethane acrylates in combination with other oligomers ormonomers;

[0326] 17. dual cure systems, which are cured first by heat andsubsequently by UV or electron irradiation, or vice versa, and whosecomponents contain ethylenic double bonds capable to react onirradiation with UV light in presence of a photoinitiator or with anelectron beam.

[0327] In addition to components (A) and (B), the coating compositionaccording to the invention preferably comprises as component (C) a knownlight stabilizer of the sterically hindered amine type, the2-(2-hydroxyphenyl)-1,3,5-triazine and/or2-hydroxyphenyl-2H-benzotriazole type as explained above, examples arementioned in the above list in sections 2.1, 2.6 and 2.8. Furtherexamples for light stabilizers of the 2-(2-hydroxyphenyl)-1,3,5-triazinetype advantageously to be added can be found e.g. in the publicationsU.S. Pat. No. 4,619,956, EP-A-434608, U.S. Pat. Nos. 5,198,498,5,322,868, 5,369,140, 5,298,067, WO-94/18278, EP-A-704437, GB-A-2297091,WO-96/28431. Of special technical interest is the addition of the2-(2-hydroxyphenyl)-1,3,5-triazines and/or2-hydroxyphenyl-2H-benzotriazoles, especially the2-(2-hydroxyphenyl)-1,3,5-triazines.

[0328] Component (C) is preferably used in an amount of 0.05-5 parts byweight per 100 parts by weight of the solid binder.

[0329] Examples of tetraalkylpiperidine derivatives which can be usedadvantageously as component (C) in coatings are given in EP-A-356 677,pages 3-17, sections a) to f). These sections of this EP-A are regardedas part of the present description. It is particular expedient to employthe following tetraalkylpiperidine derivatives:

[0330] bis(2,2,6,6-tetramethylpiperid-4-yl) succinate,

[0331] bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,

[0332] bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate,

[0333] di(1,2,2,6,6-pentamethylpiperid-4-yl)butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,

[0334] bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate,

[0335] tetra(2,2,6,6-tetramethylpiperid-4-yi)butane-1,2,3,4-tetracarboxylate,

[0336] tetra(1,2,2,6,6-pentamethylpiperid-4-yl)butane-1,2,3,4-tetracarboxylate,

[0337] 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane,

[0338]8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione,

[0339]1,1-bis-(1,2,2,6,6-pentamethylpiperidine-4-yl-oxycarbonyl)-2-(4-methoxyphenyl)-ethene,

[0340] or a compound of the formulae

[0341] in which m is 5-50.

[0342] Apart from components (A), (B) and, if used, (C), the coatingcomposition can also comprise further components, examples beingsolvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents,drying catalysts and/or levelling agents. Examples of possiblecomponents are those described in Ullmann's Encyclopedia of IndustrialChemistry, 5th Edition, Vol. Al18, pp. 429-471, VCH, Weinheim 1991.

[0343] Possible drying catalysts or curing catalysts are, for example,organometallic compounds, amines, amino-containing resins and/orphosphines. Examples of organometallic compounds are metal carboxylates,especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metalchelates, especially those of the metals Al, Ti or Zr, or organometalliccompounds such as organotin compounds, for example.

[0344] Examples of metal carboxylates are the stearates of Pb, Mn or Zn,the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or thecorresponding linoleates, resinates or tallates.

[0345] Examples of metal chelates are the aluminium, titanium orzirconium chelates of acetylacetone, ethyl acetylacetate,salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyltrifluoroacetylacetate, and the alkoxides of these metals.

[0346] Examples of organotin compounds are dibutyltin oxide, dibutyltindilaurate or dibutyltin dioctoate.

[0347] Examples of amines are, in particular, tertiary amines, forexample tributylamine, triethanolamine, N-methyldiethanolamine,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine ordiazabicyclooctane (triethylenediamine) and salts thereof. Furtherexamples are quaternary ammonium salts, for exampletrimethylbenzylammonium chloride.

[0348] Amino-containing resins are simultaneously binder and curingcatalyst. Examples thereof are amino-containing acrylate copolymers.

[0349] The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

[0350] The novel coating compositions can also be radiation-curablecoating compositions. In this case, the binder essentially comprisesmonomeric or oligomeric compounds containing ethylenically unsaturatedbonds, which after application are cured by actinic radiation, i.e.converted into a crosslinked, high molecular weight form. Where thesystem is UV-curing, it generally contains a photoinitiator as well.Corresponding systems are described in the abovementioned publicationUllmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18,pages 451-453. In radiation-curable coating compositions, the novelstabilizers can also be employed without the addition of stericallyhindered amines.

[0351] The coating compositions according to the invention can beapplied to any desired substrates, for example to metal, wood, plasticor ceramic materials. They are preferably used as topcoat in thefinishing of automobiles. If the topcoat comprises two layers, of whichthe lower layer is pigmented and the upper layer is not pigmented, thenovel coating composition can be used for either the upper or the lowerlayer or for both layers, but preferably for the upper layer.

[0352] The novel coating compositions can be applied to the substratesby the customary methods, for example by brushing, spraying, pouring,dipping or electrophoresis; see also Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 491-500.

[0353] Depending on the binder system, the coatings can be cured at roomtemperature or by heating. The coatings are preferably cured at 50-150°C., and in the case of powder coatings or coil coatings even at highertemperatures.

[0354] The coatings obtained in accordance with the invention haveexcellent resistance to the damaging effects of light, oxygen and heat;particular mention should be made of the good light stability andweathering resistance of the coatings thus obtained, for example paints.

[0355] The invention therefore also relates to a coating, in particulara paint, which has been stabilized against the damaging effects oflight, oxygen and heat by a content of the compound of the formula (I)according to the invention. The paint is preferably a topcoat forautomobiles. The invention furthermore relates to a process forstabilizing a coating based on organic polymers against damage by light,oxygen and/or heat, which comprises mixing with the coating compositiona mixture comprising a compound of the formula (I), and to the use ofmixtures comprising a compound of the formula (I) in coatingcompositions as stabilizers against damage by light, oxygen and/or heat.

[0356] The coating compositions can comprise an organic solvent orsolvent mixture in which the binder is soluble. The coating compositioncan otherwise be an aqueous solution or dispersion. The vehicle can alsobe a mixture of organic solvent and water. The coating composition maybe a high-solids paint or can be solvent-free (e.g. a powder coatingmaterial). Powder coatings are, for example, those described inUllmann's Encyclopedia of Industrial Chemistry, 5th Ed., A18, pages438-444. The powder coating material may also have the form of apowder-slurry (dispersion of the powder preferably in water). Thepigments can be inorganic, organic or metallic pigments. The novelcoating compositions preferably contain no pigments and are used as aclearcoat. Likewise preferred is the use of the coating composition as atopcoat for applications in the automobile industry, especially as apigmented or unpigmented topcoat of the paint finish. Its use forunderlying coats, however, is also possible.

[0357] The examples below illustrate the invention further. All parts orpercentages, in the examples as in the remainder of the description andin the claims, are by weight, unless stated otherwise. Room temperaturedenotes a temperature in the range 20-30° C., unless stated otherwise.Data given for elemental analysis are in % by weight calculated (cal) orexperimentally measured (exp) for the elements C, H and N. In theexamples, the following abbreviations are used: % w/w percent by weight;% w/v percent weight by volume; x % (w/v) stands for x g solid dissolvedin 100 ml liquid; m.p. melting point or range; PC polycarbonate; ABSacrylonitrile-butadiene-stryene terpolymer; POM polyoxymethylene; PPpolypropylene; LDPE low density polyethylene; DSC differential scancalorimetry; NMR nuclear magnetic resonance (of ¹H, if not otherwiseindicated).

[0358] A: PREPARATION EXAMPLES

EXAMPLE A1

[0359] Precursor compound 3,3,5,5-tetraalkyl-piperazin-2,6-dione of theformula

[0360] is obtained according to T. Yoshioka et al., Bull. Chem. Soc.Jap. 45, 1855-1860 (1972); m.p. 240-242° C.

EXAMPLE A2

[0361] In a 1 l three necked flask equipped with a stirrer, thermometer,condenser drying tube and gas inlet tube are placed 94 g of3,3,5,5-tetraalkyl-piperazin-2,6-dione (product of example A1) and 57 gof potassium tert-butoxide in 400 ml of dimethylacetamide. The reactionis slightly exothermic, the temperature rising to 55° C.; to the stirredsolution is added dropwise 77 g of ethyl-bromoacetate, and stirring iscontinued for 5 hours. The reaction mixture is cooled to roomtemperature, then after addition of 200 ml of CH₂Cl₂ is poured into 200ml of water. The organic layer is separated and concentrated underreduced pressure. The residue is dissolved in toluene, filtered andevaporated under reduced pressure. The product of the formula

[0362] is obtained as a white residue; m.p. 58-60° C.

EXAMPLE A3

[0363] The product of example A2 is charged in a 11 three necked flaskequipped with a stirrer, thermometer, condenser drying tube and gasinlet tube with 18 g of p-formaldehyde in 120 ml of tert-amylalcohol andto the reaction mixture, heated to 75° C., is added dropwise a solutionof 24 g of formic acid in 100 ml of tert-amylalcohol. The reactionmixture is heated to 85° C. and kept for 6 hours, then cooled to roomtemperature. A solution of 21 gr of NaOH in 50 ml of water is added. Theorganic layer is extracted with CH₂Cl₂, washed with water and evaporatedunder reduced pressure. The product of the formula

[0364] is collected as a white powder. Melting point: 59° C. (by DSC)

EXAMPLE A4

[0365]

[0366] The product of example A3 is charged in a 1 l three necked flaskequipped with a stirrer, thermometer, condenser drying tube and gasinlet tube with 10 g of pentaerythritol in a solution of 120 ml ofxylene. 1 g of lithium amide is added to the stirred solution at 100° C.The reaction mixture is heated slowly to 135° C. and kept at thistemperature for 24 hours, then cooled to room temperature and filteredand evaporated under reduced pressure. The residue is crystallized fromhot n-hexane yielding the above product as a white solid of meltingrange 240-244° C. Elemental Analysis calculated C = 57.0%, H = 7.4%, N =10.8% measured C = 57.2%, H = 7.3%, N = 10.7%

EXAMPLE A8

[0367]

[0368] In a three necked flask equipped with a stirrer, thermometer,condenser drying tube and gas inlet tube are placed 94 gr of3,3,5,5-tetraalkyl-piperazin-2,6-dione and 57 gr of potassiumtert-butoxide in 400 ml of dimethylacetamide. The mixture is warmed upto 55° C. and 77 gr of ethyl-bromoacetate are added dropwise understirring and left to react for additional 5 hours and cooled down to 25°C. A 200 ml portion of CH₂Cl₂ and 200 ml portion of water is added tothe mixture under stirring and the organic layer is collected, driedover Na₂SO₄ and charged, together with 400 ml of xylene and 22.8 g ofdi-ethylen glycol, in a round bottomed flask equipped with a stirrer,thermometer, condenser drying tube and gas inlet tube. The solution isheated up to reflux temperature and 0.2 g of di-buthyl tin oxide areadded to the mixture and left to react for 12 hours, then cooled down to25° C. The solution is then concentrated under vacuum and the resultingsolid is charged in a round bottomed flask equipped with a stirrer,thermometer, condenser drying tube and gas inlet tube. 350 ml oftert-amyl alcohol and 28 g of para-formaldehyde are also charged in theflask and the resulting mixture is warmed up to 75° C. and 38.5 g offormic acid is added dropwise under stirring and left to react for 3hours keeping the temperature at 75° C., then cooled to 25° C. To themixture are added under stirring 1400 ml of CH₂Cl₂ and 42.7 g of asolution of 50% NaOH in water and left to react for 1 hour at 40° C.,then it is cooled down to 25° C. A 2000 ml portion of water and a 1400ml of ethyl acetate are added to the mixture, the organic layer isseparated, dried over Na₂SO₄ and concentrated under vacuum. The titleproduct is obtained as a white powder of m.p. 59° C. (DSC).

EXAMPLE A13

[0369]

[0370] In a three necked flask equipped with a stirrer, thermometer,condenser drying tube and gas inlet tube are placed 100 gr of3,3,5,5-tetraalkyl-piperazin-2,6-dione and 66 gr of potassiumtert-butoxide in 500 ml of N,N-dimethylacetamide. The mixture is warmedup to 55° C. and 68.3 gr of 1,6-Dibromohexane are added dropwise understirring and left to react for additional 5 hours and cooled down to 25°C. A 200 ml portion of CH₂Cl₂ and 200 ml portion of water are added tothe mixture under stirring and the organic layer is collected, driedover Na₂SO₄ and evaporated under reduced pressure. The resulting solidis then charged in a round bottomed flask equipped with a stirrer,thermometer, condenser drying tube and gas inlet tube togheter with 600ml of tert-amyl alcohol and 52 g of para-formaldehyde. The mixture iswarmed up to 75° C. and 78 g of formic acid is added dropwise understirring and left to react for 3 hours keeping the temperature at 75°C., then cooled to 25° C. To the mixture are added under stirring 2000ml of CH₂Cl₂ and 74 g of a solution of 50% NaOH in water and left toreact for 1 hour at 40° C., then cooled down to 25° C. A 3000 ml portionof water and a 2000 ml of ethyl acetate are added to the mixture, theorganic layer is separated, dried over Na₂SO₄ and concentrated undervacuum. The title product is obtained as a white powder of m.p. 94° C.(DSC).

EXAMPLE A24

[0371] In a three necked flask equipped with a stirrer, thermometer,condenser are charged 80 ml of N,N-di-methyl-acetamide, 42 g of3,3,5,5-tetraalkyl-piperazin-2,6-dione and 29 g of potassiumtert-butoxide. The mixture is heated up to 40° C. under stirring, then asolution of 19 g N,N-Bis-(2-chloro-ethyl)-formamide in 15 ml ofN,N-di-methyl-acetamide is slowly added dropwise, keeping thetemperature below 80° C. and left to react for 3 hours. The reactionmixture is cooled down to 20° C., 150 ml of methylene dichloride and 120ml of water are added under stirring, the organic layer is collected,washed with additional 20 ml of water and concentrated under vacuum. Awhite solid corresponding to the formula

[0372] is collected; m.p. 137-139° C.

EXAMPLE A25

[0373] The product of example A24 is charged in a flask equipped with athermometer and a condenser, dissolved in 120 ml of 37% aqueous HCl,heated up to refluxing temperature and left to react for 3 hours. Themixture is then concentrated under vacuum, the resulting solid issuspended in 400 ml of methylene dichloride and a 20% solution of NaOHin water is added under stirring until the aqueous layer is neutral. Theorganic layer is collected, dried over sodium sulfate, and concentratedunder vacuum yielding a white solid of the formula

[0374] m.p. 102-104° C.

EXAMPLE A17

[0375]

[0376] A 20.5 g portion of the product of Example A25 is added dropwiseover a 30′ period time in a three necked flask equipped with a stirrer,thermometer, condenser, containing 100 ml of CH₂Cl₂ and 9.2 g ofcyanuric choride cooled down to 5° C. and left to react under stirringfor 3 hours. A solution of 2 g of NaOH in 8 ml of water are added to thereaction mixture and left to reach room temperature.

[0377] Additional 20.5 g portion of the compound are added to thesolution under stirring, it is heated up to refluxing temperature for 2hours, cooled down to 25° C., 10 g of K₂CO₃ are added to the reactionmixture, heated up again to refluxing temperature for 3 hours and cooleddown to 20° C. To the reaction mixture are then added 200 ml of xylene,10 g of K₂CO₃ and 7.7 g of N,N-cyclohexyl-buthyl amine and it is heatedup to 142° C. for 16 hours under stirring, cooled down to 20° C., washedwith 120 ml of water and the organic layer is collected. Evaporation ofthe solvent under vacuum yields the title product as a white solid ofm.p. 64-66° C.

EXAMPLE A21

R—NH—(CH₂)₆—N(R)—(CH₂)₆—NH—R

[0378] with R being

[0379] A 80 g portion of the product of Example A25 is added dropwiseover 30 minutes in a three necked flask equipped with a stirrer,thermometer, condenser, containing 360 ml of CH₂Cl2 and 36 g of cyanuricchoride cooled to 5° C. and left to react under stirring for 3 hours. Asolution of 8.6 g of NaOH in 9 ml of water is added to the reactionmixture and left to reach room temperature.

[0380] A 25 g portion of N,N-di-buthyl-amine is added to the solutionunder stirring, heated up to refluxing temperature for 2 hours.Subsequently, a solution of 8.6 g of NaOH in 9 ml of water is added tothe reaction mixture, left to react for 3 hours, the mixture is cooleddown to 20° C. and the organic layer is separated and washed with 140 mlof water. The organic layer is collected, the solvent evaporated and theresulting solid charged in a three necked flask equipped with a stirrer,thermometer, condenser, containing 300 ml of xylene and 14.3 g ofbis-(hexametylene)-tri-amine. The reaction mixture is then heated up to142° C. for 16 hours, cooled down to 20° C. and washed with 400 ml ofwater. The organic layer is then concentrated under vacuum obtaining awhite solid of m.p. 68-77° C.

[0381] Elemental Analysis: cal: C61.3,H8.8,N20.4

[0382] exp:C61.0,H8.7,N19.9

EXAMPLES A5-A7, A9-A12 A14-A16, A18-A20, A22 and A23

[0383] The following compounds are obtained in analogy to the methoddescribed in the above examples using the appropriate educts: exampleformula characterization A5 

m.p. 120° C. (DSC) A6 

m.p. 100° C. (DSC) A7 

m.p. 97° C. (DSC) A9 

m.p. 99° C. (DSC) A10

m.p. 75° C. (DSC) A11

m.p. 180° C. (DSC) A12

m.p. 156° C. (DSC) A14

m.p. 286° C. (DSC) A15

m.p. 127° C. (DSC) A16

m.p. 54-58° C. A18

m.p. 190° C. (DSC) A19

m.p. 78° C. (DSC) A20

¹H-NMR (300 MHz, CDCl₃)/ppm: 3.72 (t, 4H); 2.32 (s, 6H); 1.48 (m, 4H);1.36 (s, 24 H); 1,24 (M, 12 H) A22 R—NH—(CH₂)₆—N(R)—(CH₂)₆—NH—R with Rbeing m.p. 66-72° C.

Elemental Analysis: cal:C62.3, H9.0, N19.6; exp:C61.7, H8.9, N19.2 A23

¹H-NMR (300 MHz, CDCl₃)/ppm: 3.69 (t, 4H); 3.58 (m, 2H); 2.4 (m, 4H);1.73 (m, 4H); 1.45 (m, 26 H); 1.22 (m, 26 H).

[0384] B: Application Examples

EXAMPLE B1

[0385] Light-stabilizing action in polypropylene plaques.

[0386] 1 g each of the compounds indicated in Table 1 and 1 g oftris(2,4-di-t-butylphenyl)phosphite, 0.5 g of pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxy phenyl)propionate], 1 g of calcium stearateand 1 g of Filofin Blue 4G are mixed in a turbo mixer with 1000 g ofpolypropylene powder (MOPLEN™ SSF) of melt index=3.7 g/10 minutes(measured at 230° C. an 2.16 kg).

[0387] The mixtures obtained are extruded at a temperature of 200-230°C. to give polymer granules which are then converted into plaques of 2mm thickness by injection moulding at 200-220° C. The plaques obtainedare exposed in a model 65 WR Weather-O-Meter (ASTM D2565-85) with ablack panel temperature of (63±3)° C. until surface embrittlement(chalking) starts. Further samples are exposed until a roughnessparameter Ra=0.5 μm is reached; evaluation is done using a measurementunit for surface texture (Surtronic™ model 3+; Lc=0.8 mm; Ln=4.0 mm, Lcbeing the cut-off length, i.e. the lenght of the reference line used foridentifying the irregularities characterising the surface and Ln beingthe total evaluation length).

[0388] A plaque of polypropylene prepared under the same conditions asindicated above but without the addition of the compounds of theinvention is exposed for comparison. TABLE 1 In Table 1, the exposuretime needed is given in hours. The longer the time the better is thestabilizing effect. R_(a) = 0.5 μm after Chalking time Stabilizer(hours) (hours) without stabilizer  500 compound of Example A12 32003450 compound of Example A13 4090 4020 compound of Example A16 3580 3450

EXAMPLE B2

[0389] Light-stabilizing action in polypropylene tapes.

[0390] 1 g of each of the compounds listed in Table 2, 1 g oftris[2,4-di-tert-butylphenyl]phosphite, 0.5 g of pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate] and 1 g ofcalcium stearate are mixed in a turbomixer with 1000 g of polypropylenepowder (MOPLEN™ SSF, having a melt index of 3.7 measured at 230° C. and2.16 kg).

[0391] The mixtures are extruded at 200-220° C. to give polymer granuleswhich are subsequently converted to stretched tapes of 50 μm thicknessand 2.5 mm width, using a semi-industrial type of apparatus(®Leonard-Sumirago (VA)—Italy) and waking under the followingconditions: Extruder temperature: 200-230° C. Head temperature: 240-260°C. Stretch ratio: 1:6

[0392] The tapes thus prepared are mounted on a white card and exposedin a Weather-O-Meter 65 WR (ASTM D 2565-85) with a black paneltemperature of (63±3)° C.

[0393] The residual tenacity is measured, by means of a constantvelocity tensometer, on a sample taken after various light exposuretimes; from this, the exposure time (in hours) required to halve theinitial tenacity (T₅₀) is measured.

[0394] By way of comparison, tapes prepared under the same conditions asindicated above, but without the addition of the stabilizers of thepresent invention, are exposed. The results are shown in Table 2. TABLE2 Stabilizer T₅₀ (hours) without stabilizer  500 compound of Example A81640 compound of Example A10 1610 compound of Example A13 2110 compoundof Example A16 1910

EXAMPLE B3

[0395] Light-stabilizing action in polypropylene fibers.

[0396] 1 g of the compound indicated in table 3 below together with 1 gof calcium stearate, 2.5 g of TiO₂ (Kronos™ RN 57) and a blend of 0.5gof calcium monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate and0.5 g of tris(2,4-di-tert-butylphenyl) phosphite are mixed with 1000 gof polypropylene powder (Moplen™ FLF 20; melt flow index 12.2 g/10 min,measured at 230° C. and 2.16 kg) in a turbo mixer.

[0397] The mixtures are extruded at 190-230° C. to give granules; theseare subsequently converted into fibres using a a semi-industrial type ofapparatus (Leonard-Sumirago™ (VA), Italy) under the followingconditions: Extruder temperature: 200-230° C. Head temperature: 255° C.Stretch ratio:   1:3.5 Count: 11 dtex per filament

[0398] The fibres produced in this way are exposed against a whitecardboard in a Weather-O-Meter™ Type 65WR with a black panel temperatureof (63±3)° C. in accordance with ASTM D 2565-85. After various exposuretimes, the residual tensile strength of the samples is measured by meansof a constant-speed tensometer. The exposure time T₅₀ needed to halvethe initial tensile strength is then calculated. The results are shownin Table 3 below. The amount data are based on the weight of thepolypropylene employed. TABLE 3 Exposure duration (T₅₀/h) for thetensile strength to half Stabilizer T₅₀/h none  300 A21 1100 A22 1280

[0399] The fibres stabilized according to the invention have excellenttenacity.

EXAMPLE B4

[0400] Stabilization of polyethylene films

[0401] The additives reported in table 4 below are mixed via masterbatchwith LDPE pellets (Riblene™ FF 29; d=0.921g/cm; MFI (190° C./2.16kg)=0.60 g/10 min.) in a turbo mixer. The mixtures are extruded at 200°C. to obtain granules that are converted into films of thickness 150 μmby compression molding (170° C./3 min.).

[0402] Some of the films are treated with pesticides by storing thembefore WOM exposure for 20 days at 30° C. over a concentrated solutionof VAPAMTM in water (1:1 relation in parts by volume) without directcontact with the solution.

[0403] VAPAM™ (BASLINI SpA, Treviglio/BG, Italy) is an aqueous solutionof 382 g per liter of metam-sodium having the formula CH₃—NH—CS—SNa.

[0404] Film samples are then mounted in quartz tubes and exposed againsta white cardboard in a Weather-O-Meter™ (WOM) Type 65 WR with a blackpanel temperature of (63±3)° C. The degradation process is monitored bymeasuring the increase of carbonyl in the sample with a FourierTransform Infrared Spectrophotometer. A high increase of carbonylindicates high degradation. The results are given in the following table4 (arbitrary units). The amount data are based on the weight of thepolyethylene employed. TABLE 4 Increase of carbonyl concentration (iCO)after the indicated exposure (WOM) iCO after pesticide Stabilizer iCOafter 875 h WOM treatment and 765 h WOM none 0.4 0.8 0.3% A21 0.0370.072 0.3% A22 0.046 0.078

[0405] It is evident, that the stabilizer of the invention provideseffective stabilization for PE films both with and without pesticidetreatment.

EXAMPLE B5

[0406] Stabilization of a gray pigmented polycarbonate/ABS blend.

[0407] Commercial PC/ABS-blend (Cycoloy™ MC 8002; 50/50 wt/wt blend ofPC and ABS pigmented with 1% by weight of Gray 9779 is stabilized byaddition of 1% by weight of2-(2′-hydroxy-3′,5′-bis(1,1-dimethylbenzyl)phenyl)-benztriazole (C) and0.5% by weight of the compound indicated in table 5. A sample containingonly the 1% by weight of the benztriazole stabilizer and an unstabilizedsample serve as comparison. Izod bars (2.5″L×0.5″W×0.125″W) are preparedby injection molding on a BOY 30 machine, barrel temperature 475-515°F., die temperature 515° F. Accelerated weathering is performed using anAtlas Ci65A Weather-o-meter (XAW), operated in either “Dry XAW” mode(ASTM G26-90 method C). After regular intervals, the color change ΔEaccording to DIN 6174 is determined. Results are compiled in table 5.TABLE 5 Color change (ΔE) of gray pigmented PC after the indicatedirradiance time Irradiance time: 94.8 h 500.5 h 999.7 h 1249.0 hStabilizer ΔE ΔE ΔE ΔE none 1.5 6.9 9.8 11.0 C 0.7 4.2 7.7 9.0 C + A110.5 3.1 6.2 7.2 C + A14 0.2 2.3 5.4 7.0 C + A4 0.3 2.1 5.0 6.5 C + A170.3 1.7 4.3 5.7

EXAMPLE B6

[0408] Stabilization of a white pigmented polycarbonate/ABS blend.

[0409] Samples are prepared from commercial PC/ABS-blend (Cycoloy™ MC8002; 50/50 wt/wt blend of PC and ABS as described in example B5 exceptthat TiO₂ (TionaTM RCL-4 rutile; SCM chemicals) is used as pigment.Weathering and assessment is done as described in example B5; resultsare compiled in table 6. TABLE 6 Color change (ΔE) of white pigmented PCafter the indicated irradiance time Irradiance time: 499.3 h 999.8 h1249.3 h Stabilizer ΔE ΔE ΔE none 11.6 21.8 23.7 C 6.0 15.7 17.4 C + A112.6 10.2 11.7 C + A14 2.3 9.3 11.3 C + A4 2.7 9.6 11.4 C + A17 2.2 9.210.7

[0410] PC/ABS samples stabilized according to the invention show anexcellent color stability.

EXAMPLE B7

[0411] Gloss and Chip Impact Strength of stabilized PC/ABS

[0412] Further samples prepared and exposed to weathering as shown inexamples B5 and B6 are assessed in respect of gloss and chip impactstrength.

[0413] Gloss: 2″×2″ injection molded plaques are removed and replaced ateach interval. Measurement device is BYK-Gardner Haze-Gloss LaboratoryReference Instrument.

[0414] Chip impact testing: 10 replicate bars are used for each testinterval, impacting the exposed face. Test conducted per ASTM D4508-90using TMI Monitor/impact Tester. PC/ABS samples stabilized according tothe invention with 0.5% by weight of the compound of example A4 or A17show excellent gloss retention and impact strength.

EXAMPLE B8

[0415] Stabilization of a 2-coat metallic finish

[0416] The light-stabilizers to be tested are dissolved in 30 g ofSolvesso®100 and tested in a clearcoat having the following composition(parts by weight): Synthacryl ® SC 303¹⁾ 27.51 Synthacryl ® SC 370²⁾23.34 Maprenal ® 650³⁾ 27.29 Butyl acetate/Butanol (37/8) 4.33Isobutanol 4.87 Solvesso ® 150⁴⁾ 2.72 Crystal Oil K-30⁵⁾ 8.74 Levellingassistant Baysilon ® MA⁶⁾ 1.20 100.00

[0417] 1% of the light-stabilizers to be tested is added to theclearcoat, based on the solids content of the varnish. For comparison, aclearcoat containing no light-stabilizers is used. The clearcoat isdiluted with Solvesso® 100 to spray viscosity and is applied by sprayingto a prepared aluminium panel (®Uniprime Epoxy, silver-metallicbasecoat) which is baked at 130° C., for 30 minutes, to give a dry filmthickness of 40-50 μm of clearcoat.

[0418] The samples are then weathered in an Atlas ®UVCON weathering unit(UVB-313 lamps) in a cycle comprising UV irradiation at 70° C. for 4hours and condensation at 50° C. for 4 hours. The surface gloss (20°gloss as defined in DIN 67530) of the samples is then measured atregular intervals. The results are shown in Table 8. TABLE 8 20° * glossas defined in DIN 67530 after . . . hours weathering in the ®UVCON(UVB-313) Light-stabilizer 0 hours 400 hours None 93 77 A7 93 83 A8 9385 A9 93 86 A10 93 81 A12 93 86 A13 93 89

[0419] The results listed in Table 8 show that the samples stabilizedwith a stabilizer according to the invention have better weatheringstability (gloss retention) than the unstabilized sample.

EXAMPLE B9

[0420] Stabilization of Thermoplastic Olefins

[0421] Molded test specimens are prepared by injection moldingthermoplastic olefin (TPO) pellets containing pigments, a phosphite, aphenolic antioxidant or hydroxylamine (HA), a metal stearate,ultraviolet light absorbers (UVA) or a hindered amine stabilizers (HALS)or a mixture of UV absorbers and hindered amine stabilizers as describedbelow.

[0422] Pigmented TPO pellets are prepared from pure pigment or pigmentconcentrates, stabilizers, co-additives and commercially availablethermoplastic olefin by mixing the components in a Superior/MPM 1″single screw extruder with a general all-purpose screw (24:1 UD) at 400°F. (200° C.), cooled in a water bath and pelletized. The resultingpellets are molded into 60 mil (0.006 inch thick) 2″×2″ plaques at about375° F. (190° C.) on a BOY 30M Injection Molding Machine.

[0423] Pigmented TPO formulations composed of polypropylene blended witha rubber modifier where the rubber modifier is an in-situ reactedcopolymer or blended product containing copolymers of propylene andethylene with or without a ternary component such as ethylidenenorbornene are stabilized with a base stabilization system consisting ofan N,N-dialkylhydroxylamine or a hindered phenolic antioxidant with orwithout an organophosphorous compound.

[0424] All additive and pigment concentrations in the final formulationsare expressed as weight percent based on the resin.

[0425] Formulations contain thermoplastic olefin pellets and one or moreof the following components;

[0426] 0.0% -2.0% pigment,

[0427] 0.0% -50.0% talc

[0428] 0.0% -0.1% phosphite,

[0429] 0.0% -1.25% phenolic antioxidant,

[0430] 0.0% -0.1% hydroxylamine,

[0431] 0.05% -0.10% calcium stearate,

[0432] 0.0% -1.25% UV absorber,

[0433] 0.0% -1.25% hindered amine stabilizer (HALS).

[0434] The components are dry blended in a tumble dryer prior toextrusion and molding.

[0435] Test plaques are mounted in metal frames and exposed in an AtlasCi65 Xenon Arc Weather-o-meter at 70° C. black panel temperature, 0.55W/m² at 340 nanometers and 50% relative humidity with intermittentlight/dark cycles and water spray (Society of Automotive Engineers—SAE J1960 Test Procedure). Specimens are tested at approximately 625kilojoule intervals by performing color measurements on an Applied ColorSystems spectrophotometer by reflectance mode according to ASTM D2244-79. Data collected include delta E, L*, a* and b* values. Glossmeasurements are conducted on a BYK-GARDNER Haze/Gloss Meter at 60°according to ASTM D523.

[0436] UV Exposure Testing

[0437] Test specimens prepared from a commercially available polyolefinblend (Polytrope TPP 518-01; commercial supplier A. Schulman, Inc.;Akron, Ohio, U.S.A.) as 60 mil thick 2″×2″ injection molded plaques areexposed to UV radiation under SAE J 1960—Exterior Automotive conditions.

[0438] The Control sample contains as stabilizer formulation thecompound A as indicated in the following table, 0.2% by weight ofcompound B and 0.1% of a 1:1 mixture oftris(2,4-di-t-butylphenyl)phosphite and 1 part of pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] in the finalresin formulation as commonly used in the industry to impart UVstability.

[0439] Samples 1-3 stabilized according to the invention contain 0.05%dialkylhydroxylamine in the final resin formulation as basestabilization and 0.2% by weight of compound C costabilizer. Compound Ais Bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate;

[0440] compound B is Poly [[6-[(1,1,3,3-tetramethyl butyl)amino]-1,3,5-triazine-2,4-diyl][[(2,2,6,6-tetramethyl-4-piperidyl)imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]]; CAS-No.70624-18-9; compound C is of the formulaR—NH—(CH₂)₃—N(R)—(CH₂)₂—N(R)—(CH₂)₃—NH—R, with R being

[0441] (CAS-No. 106990-43-6). Compounds A, B and C are commercialstabilizers (Ciba Specialty Chemicals Inc.).

[0442] All of the samples contain talc at 15%,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole at 0.2%, 0.1%calcium stearate and as color package 0.25% Red 3B and Pigment Red 177,C.I. # 65300.

[0443] All additive and pigment concentrations in the final formulationsare expressed as weight percent on the resin. TABLE 9 UV exposuretesting of Polytrope TPP plaques delta E Gloss % Gloss Retention SampleHALS 3000 Kj/m² 3000 Kj/m² 3000 Kj/m² Control 0.20% A 4.7 5.4 8.1% 10.20% A9 1.9 21.8 32.1% 2 0.20% A19 2.2 27.2 40.6% 3 0.20% A13 2.3 15.927.3%

What is claimed is:
 1. A composition comprising (A) a synthetic organicpolymer selected from the group consisting of polyoxymetbylene, a blendof polycarbonate with acrylonitrile-butadiene-styrene terpolymer, and acoating system based on a functional acrylate resin and a crosslinkingagent, and (B) as stabilizer a compound of the formula I or II

wherein p is from the range 1 to 10; s is from the range 1 to 8; when sis 1, A is C₁-C₁₈alkyl; C₂-C₁₈alkyl which is substituted by NH₂,hydroxy, halogen and/or OR₁₀ or interrupted by —O—, —NH— and/or —NR₁₀—;or A is C₁-C₁₈alkyl substituted by —COOR₁₁ or phenyl; when s is 2, A isC₂-C₁₀alkylene; C₄-C₁₂alkenylene; C₃-C₁₅alkylene substituted by OHand/or interrupted by oxygen, phenylene, C₁-C₄alkylphenylene, —COO—,—CONH—,

when s is 3, A is C₃-C₁₀alkantriyl; C₃-C₁₂alkantriyl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or a group of a formula(IIIa)-(IIId)

when s is 4, A is C₄-C₁₀alkantetryl; C₄-C₁₂alkantetryl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (IVa)-(IVd)

when s is 5, A is C₅-C₁₀alkanepentayl; C₅-C₁₂alkanepentayl substitutedby OH and/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groupsof the formulae (Va)-(Vc)

when s is 6, A is C₆-C₁₀alkanehexayl; C₆-C₁₂alkanehexayl substituted byOH and/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIa)-(VIf)

when s is 7, A is C₇-C₁₀alkaneheptayl; C₇-C₁₂alkaneheptayl substitutedby OH and/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groupsof the formulae (VIIa)-(VIId)

when s is 8, A is C₈-C₁₀alkaneoctayl; C₈-C₁₂alkaneoctayl substituted byOH and/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIIIa)-(VIIIb)

the index i is zero or 1; R₁, R₂, R₃ and R₄, independently of eachother, are C₁-C₄alkyl, or R₁ and R₂ or R₃ and R₄, together with thecarbon atom to which they are bound, form a cyclopentyl or cyclohexylring; R₅ is hydrogen; C₁-C₁₈alkyl; oxyl; OH; CH₂CN; C₁-C₁₈alkoxy;C₅-C₁₂cycloalkoxy; C₃-C₈alkenyl; C₃-C₈alkynyl; C₇-C₁₂phenylalkyl;C₇-C₁₅phenylalkyl, which is substituted on the phenyl ring by 1, 2 or 3radicals selected from C₁-C₄alkyl and C₁-C₄alkoxy; C₇-C₁₅phenylalkoxy;C₇-C₁₅phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3radicals selected from C₁-C₄alkyl and C₁-C₄alkoxy; or R₅ isC₁-C₈alkanoyl; C₃-C₅alkenoyl; C₁-C₁₈alkanoyloxy; glycidyl; or a group—CH₂CH(OH)—G, in which G is hydrogen, methyl or phenyl; R₈ and R₉, andR₂₈, R₂₉, R₃₀, R₃₁, R₃₂ and R₃₃, independently of each other, areC₁-C₄alkylene; R₁₀ is C₁-C₈alkyl, C₁-C₈alkanoyl, C₅-C₁₂cycloalkyl,C₇-C₁₅phenylalkyl which is unsubstituted or substituted on the phenylring by a radical selected from C₁-C₄alkyl and Cl-C₄alkoxy; or R₁₀ isC₁-C₈alkyl or C₁-C₈alkanoyl substituted by OH, C₁-C₁₂alkoxy and/or aresidue benzophenonyl or benzophenonyloxy, wherein one or both phenylrings of the benzophenone moiety are unsubstituted or substituted by OH,halogen, C₁-C₄alkyl and/or C₁-C₁₈alkoxy; R₁₁ is C₁-C₁₈alkyl; C₂-C₁₈alkylwhich is substituted by NH₂, NHR₁₀, N(R₁₀)₂, nitro, hydroxy and/orC₁-C₁₈alkoxy; C₃-C₁₈alkenyl; C₅-C₁₂cycloalkyl; C₅-C₁₂cycloalkyl which issubstituted by C₁-C₄alkyl and/or interrupted by —O—; R₁₅ and R′₁₅,independently of each other, are is C₂-C₁₀alkylene; C₃-C₁₂alkylenesubstituted by OH and/or interrupted by oxygen, phenylene,C₁-C₄alkylphenylene, —NH— or —NR₁₀—; R₁₆ is C₃-C₁₀alkantriyl;C₃-C₁₂alkantriyl substituted by OH and/or interrupted by oxygen, —NH— or—NR₁₀—; R₁₇ is C₄-C₁₀alkantetryl; C₄-C₁₂alkantetryl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; R₁₈ isC₅-C₁₀alkanepentayl; C₅-C₁₂alkanepentayl substituted by OH and/orinterrupted by oxygen, —NH— or —NR₁₀—; R₁₉ is C₆-C₁₀alkanehexayl;C₆-C₁₂alkanehexayl substituted by OH and/or interrupted by oxygen, —NH—or —NR₁₀—; X is —O—, —NH— or —N(R₁₀)—; X₁, X₂, X₃, X₄, X₅, X₆, X₇ andX₈, independently of each other, are —O— or —NH—; Y is —O— or a residueof the formula

Z stands for halogen, NH₂, NHR₁₀, N(R₁₀)₂ or C₁-C₄alkoxy; Z₁ has one ofthe meanings given for Z or is —X—R′₁₅—XH and Z₂ is H or a residue ofthe formula


2. A composition according to claim 1, wherein the blend ofpolycarbonate with acrylonitrile-butadiene-styrene terpolymer ofcomponent (A) is a blend of 10 to 90 parts by weight of polycarbonatewith 90 to 10 parts by weight of acrylonitrile-butadiene-styreneterpolymer.
 3. A composition according to claim 1 containing as furthercomponent (C) a UV absorber from the class of the benzotriazoles,o-hydroxyphenyl-s-triazines and/or benzophenones.
 4. A compositionaccording to claim 1, wherein in the compound of formula I (component B)wherein s is from the range 2 to 6; when s is 2 A is C₂-C₁₀alkylene;C₃-C₁₂alkylene substituted by OH and/or interrupted by oxygen, —NH— or—NR₁₀—; or a group of the formula —R₈—COO—R₁₂—OCO—R₉— (IIa); when s is3, A is a group of the formula (IIIa)

when s is 4, A is one of the groups of the formulae (IVa) or (IVd)

when s is 5, A is a group of the formula (Va)

when s is 6, A is one of the groups of the formulae (VIb)-(VIf)

the index i is zero or 1; R₁, R₂, R₃ and R₄, independently of eachother, are methyl; R₅ is hydrogen; C₁-C₁₈alkyl; oxyl; OH; C₁-C₁₈alkoxy;C₅-C₁₂cycloalkoxy; C₃-C₈alkenyl; or R₅ is C₁-C₈alkanoyl; C₃-C₅alkenoyl;C₁-C₁₈alkanoyloxy; glycidyl; or a group —CH₂CH(OH)—G, in which G ishydrogen, methyl or phenyl; R₈ and R₉, and R₂₈, R₂₉, R₃₀, R₃₁, R₃₂ andR₃₃, independently of each other, are methylene; R₁₀ is C₁-C₈alkyl,C₁-C₈alkanoyl, C₅-C₁₂cycloalkyl; R₁₂ is C₂-C₁₀alkylene; orC₃-C₁₂alkylene interrupted by oxygen, —NH— or —NR₁₀—; R₁₅ and R′₁₅,independently of each other, are is C₂-C₁₀alkylene; R₁₇ isC₄-C₁₀alkantetryl; R₁₈ is C₅-C₁₀alkanepentayl; X is —O—, —NH— or—N(R₁₀)—; X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈, independently of eachother, are —O— or —NH—; and Z stands for NHR₁₀, N(R₁₀)₂ or C₁-C₄alkoxy.5. A compound of the formula (I′) or (II)

wherein p is from the range 1-10; s is from the range 1 to 8; R₁, R₂, R₃and R₄, independently of each other, are C₁-C₄alkyl; R₅ is hydrogen;C₁-C₁₈alkyl; oxyl; OH; CH₂CN; C₁-C₁₈alkoxy; C₅-C₁₂cycloalkoxy;C₃-C₈alkenyl; C₃-C₈alkynyl; C₇C₁₂phenylalkyl; C₇-C₁₅phenylalkyl, whichis substituted on the phenyl ring by 1, 2 or 3 radicals selected fromC₁-C₄alkyl and C₁-C₄alkoxy; C₇-C₁₅phenylalkoxy; C₇-C₁₅phenylalkoxy,which is substituted on the phenyl ring by 1, 2 or 3 radicals selectedfrom C₁-C₄alkyl and C₁-C₄alkoxy; or R₅ is C₁-C₈alkanoyl; C₃-C₅alkenoyl;C₁-C₁₆alkanoyloxy; glycidyl; or a group —CH₂CH(OH)—G, in which G ishydrogen, methyl or phenyl; when s is 1, A is C₂-C₁₈alkylene substitutedby OR₃₀, wherein R₃₀ is C₁-C₈alkyl or C₁-C₈alkanoyl substituted by aresidue benzophenonyl or benzophenonyloxy, wherein one or both phenylrings of the benzophenone moiety are unsubstituted or substituted by OH,halogen, C₁-C₄alkyl and/or C₁-C₁₈alkoxy; when s is 2 A is C₃-C₁₅alkylenesubstituted by OH and/or interrupted by oxygen,

—NH— and/or —NR₁₀—; or A is C₃-C₁₅alkylene substituted by OH andinterrupted by phenylene, C₁-C₄alkylphenylene, —COO—, —CONH—; or A isC₄-C₁₂alkenylene or one of the groups of the formulae (IIa)-(IIe)—R₈—COO—R₁₂—OCO—R₉—;  (IIa) —R₈—CONH—R₁₃—NHCO—R₉—;  (IIb)—R₈—COO—R₁₄—NHCO—R₉—;  (IIc)

and when R₅ is not hydrogen, A also embraces C₂-C₁₀alkylene;C₂-C₁₀alkylene interrupted by phenylene or C₁-C₄alkylphenylene; when sis 3, A is C₃-C₁₀alkantriyl; C₃-C₁₂alkantriyl substituted by OH and/orinterrupted by oxygen, —NH— or —NR₁₀—; or one of the groups of theformulae (IIIa)-(IIId)

when s is 4, A is C₄-C₁₀alkantetryl; C₄-C₁₂alkantetryl substituted by OHand/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (IVa)-(IVd)

when s is 5, A is C₅-C₁₀alkanepentayl; C₅-C₁₂alkanepentayl substitutedby OH and/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groupsof the formulae (Va)-(Vc)

when s is 6, A is C₆-C₁₀alkanehexayl; C₆-C₁₂alkanehexayl substituted byOH and/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIa)-(VIf)

when s is 7, A is C₇-C₁₀alkaneheptayl; C₇-C₁₂alkaneheptayl substitutedby OH and/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groupsof the formulae (VIIa)-(VIId)

when s is 8, A is C₈-C₁₀alkaneoctayl; C₈-C₁₂alkaneoctayl substituted byOH and/or interrupted by oxygen, —NH— or —NR₁₀—; or one of the groups ofthe formulae (VIIIa)-(VIIIb)

the index i is zero or 1; R₈ and R₉, and R₂₈, R₂₉, R₃₀, R₃₁, R₃₂ andR₃₃, independently of each other, are methylene, and when R₅ is nothydrogen, additionally embrace ethylene; R₁₀ is C₁-C₈alkyl,C₁-C₈alkanoyl, C₅-C₁₂cycloalkyl, C₇-C₁₅phenylalkyl which isunsubstituted or substituted on the phenyl ring by a radical selectedfrom C₁-C₄alkyl and C₁-C₄alkoxy; R₁₂, R₁₃ and R₁₄, independently of eachother, are C₂-C₁₀alkylene; C₃-C₁₂alkylene substituted by OH and/orinterrupted by oxygen, phenylene, C₁-C₄alkylphenylene, —NH— or —NR₁₀—;C₄-C₁₂alkenylene; R₁₅ and R′₁₅, independently of each other, are isC₂-C₁₀alkylene; C₃-C₁₂alkylene substituted by OH and/or interrupted byoxygen, phenylene, C₁-C₄alkylphenylene, —NH— or —NR₁₀—; R₁₆ isC₃-C₁₀alkantriyl; C₃-C₁₂alkantriyl substituted by OH and/or interruptedby oxygen, —NH— or —NR₁₀—; R₁₇ is C₄-C₁₀alkantetryl; C₄-C₁₂alkantetrylsubstituted by OH and/or interrupted by oxygen, —NH— or —NR₁₀—; R₁₈ isC₅-C₁₀alkanepentayl; C₅-C₁₂alkanepentayl substituted by OH and/orinterrupted by oxygen, —NH— or —NR₁₀—; R₁₉ is C₆-C₁₀alkanehexayl;C₆-C₁₂alkanehexayl substituted by OH and/or interrupted by oxygen, —NH—or —NR₁₀—; X is —O—, —NH— or —N(R₁₀)—; X₁, X₂, X₃, X₄, X₅, X₆,independently of each other, are —O— or —NH—; Y is —O— or a residue ofthe formula

Z stands for halogen, NH₂, NHR₁₀, N(R₁₀)₂ or C₁-C₄alkoxy; Z₁ has one ofthe meanings given for Z or is —X—R′₁₅—XH and Z₂ is H or a residue ofthe formula


6. Compound of the formula (I′) or (II) according to claim 5 wherein pis from the range 2 to 6; s is from the range 2 to 8; R₁, R₂, R₃ and R₄,independently of each other, are methyl or ethyl; R₅ is hydrogen;C₁-C₁₈alkyl; oxyl; OH; CH₂CN; C₁-C₁₈alkoxy; C₅-C₁₂cycloalkoxy;C₃-C₈alkenyl; C₇-C₁₂phenylalkyl; C₇-C₁₅phenylalkoxy; or R₅ isC₁-C₈alkanoyl; C₃-C₅alkenoyl; C₁-C₁₈alkanoyloxy; glycidyl; or a group—CH₂CH(OH)—G, in which G is hydrogen, methyl or phenyl; when s is 2 A isC₃-C₁₂alkylene substituted by OH and/or interrupted by oxygen, —NH— or—NR₁₀—; C₄-C₁₂alkenylene; or one of the groups of the formulae(IIa)-(IIe)

and when R₅ is not hydrogen, A also embraces C₂-C₁₀alkylene;C₂-C₁₀alkylene interrupted by phenylene or C₁-C₄alkylphenylene; when sis 3, A is C₃-C₁₀alkantriyl; or one of the groups of the formulae(IIIa)-(IIId)

when s is 4, A is C₄-C₁₀alkantetryl; or one of the groups of theformulae (IVa)-(IVd)

when s is 5, A is C₅-C₁₀alkanepentayl; or a group of the formula (Va)

when s is 6, A is C₆-C₁₀alkanehexayl; or one of the groups of theformulae (VIb)-(VIf)

when s is 7, A is C₇-C₁₀alkaneheptayl; when s is 8, A isC₈-C₁₀alkaneoctayl; or one of the groups of the formulae(VIIIa)-(VIIIb); the index i is zero or 1; R₈ and R₉, and R₂₈, R₂₉, R₃₀,R₃₁, R₃₂ and R₃₃, independently of each other, are methylene; R₁₀ isC₁-C₈alkyl, C₁-C₈alkanoyl, C₅-C₁₂cycloalkyl, C₇-C₁₅phenylalkyl; R₁₂, R₁₃and R₁₄, independently of each other, are C₂-C₁₀alkylene; C₃-C₁₂alkylenesubstituted by OH and/or interrupted by oxygen, —NH— or —NR₁₀—;C₄-C₁₂alkenylene; R₁₅ and R′₁₅, independently of each other, are isC₂-C₁₀alkylene; C₃-C₁₂alkylene substituted by OH and/or interrupted byoxygen, phenylene, C₁-C₄alkylphenylene, —NH— or —NR₁₀—; R₁₆ isC₃-C₁₀alkantriyl; R₁₇ is C₄-C₁₀alkantetryl; R₁₈ is C₅-C₁₀alkanepentayl;X is —O—, —NH— or —N(R₁₀)—; X₁, X₂, X₃, X₄, X₅, independently of eachother, are —O— or —NH—; and Z stands for halogen, NH₂, NHR₁₀, N(R₁₀)₂ orC₁-C₄alkoxy.
 7. Compound of the formula (I′) according to claim 5wherein s is from the range 2 to 6; R ₁, R₂, R₃ and R₄, independently ofeach other, are methyl or ethyl; R₅ is hydrogen; C₁-C₁₈alkyl; oxyl; OH;CH₂CN; C₁-C₁₈alkoxy; C₅-C₁₂cycloalkoxy; C₃-C₈alkenyl; C₇-C₁₂phenylalkyl;C₇-C₁₅phenylalkoxy; or R₅ is C₁-C₈alkanoyl; C₃-C₅alkenoyl;C₁-C₁₈alkanoyloxy; glycidyl; or a group —CH₂CH(OH)—G, in which G ishydrogen, methyl or phenyl; when s is 2 A is C₃-C₁₂alkylene substitutedby OH and/or interrupted by oxygen, —NH— or —NR₁₀—; C₄-C₁₂alkenylene; ora group of the formula (IIa) R₈—COO—R₁₂—OCO—R₉—;   (IIa) and when R₅ isnot hydrogen, A also embraces C₂-C₁₀alkylene; when s is 3, A isC₃-C₁₀alkantriyl; or one of the groups of the formulae (IIa), (IIIb) or(IIId); when s is 4, A is C₄-C₁₀alkantetryl; or one of the groups of theformulae (IVa), (IVb) or (IVd); when s is 5, A is C₅-C₁₀alkanepentayl;when s is 6, A is one of the groups of the formulae (VIb)-(VIf); theindex i is zero or 1; R₈ and R₉, and R₂₈, R₂₉, R₃₀, R₃₁, R₃₂ and R₃₃,independently of each other, are methylene; R₁₀ is C₁-C₈alkyl,C₁-C₈alkanoyl, C₅-C₁₂cycloalkyl; R₁₂ is C₂-C₁₀alkylene; C₃-C₁₂alkylenesubstituted by OH and/or interrupted by oxygen, —NH— or —NR₁₀—; R₁₅ andR′₁₅, independently of each other, are is C₂-C₁₀alkylene; R₁₆ isC₃-C₁₀alkantriyl; R₁₇ is C₄-C₁₀alkantetryl; X is —O—, —NH— or —N(R₁₀)—;X₁, X₂, X₃, X₄, independently of each other, are —O— or —NH—; and Zstands for NHR₁₀ or N(R₁₀)₂.
 8. Compound of the formula (I′) accordingto claim 5 wherein s is 2, 3, 4 or 6; R₁, R₂, R₃ and R₄ are methyl; R₅is hydrogen; C₁-C₈alkyl; C₁-C₁₈alkoxy; cyclohexyloxy; allyl; benzyl;acetyt C₃-C₄alkenoyl; glycidyl; when s is 2 A is C₃-C₁₀alkylenesubstituted by OH or interrupted by oxygen, —NH— or —NR₁₀—; or a groupof the formula —R₈—COO—R₁₂—OCO—R₉— (IIa); and when R₅ is not hydrogen, Aalso embraces C₂-C₁₀alkylene; when s is 3, A is a group of the formula(IIIa); when s is 4, A is a group of the formula (IVa) or (IVd); when sis 6, A is a groups of the formula (VIe); the index i is zero; R₈ andR₉, and R₂₈, R₂₉, R₃₀, R₃₁, R₃₂ and R₃₃ are methylene; R₁₀ isC₁-C₈alkyl, formyl, acetyl, or cyclohexyl; R₁₂ is C₂-C₁₀alkylene; orC₃-C₁₀alkylene interrupted by oxygen; R₁₅ and R′₁₅, independently ofeach other, are is C₂-C₁₀alkylene; R₁₇ is C₄-C₁₀alkantetryl; X is —NH—;X₁, X₂, X₃, X₄ are —O—; and Z stands for N(R₁₀)₂.
 9. A compositioncomprising A) an organic material sensitive to damage by light, oxygenand/or heat, and B) as stabilizer a compound of the formula I′ or IIaccording to claim
 5. 10. A composition according to claim 9 comprisingas organic material a thermoplastic organic polymer or a binder for acoating or a photographic material.
 11. A composition according to claim9 comprising from 0.1 to 10% by weight, based on the material to bestabilized, of the stabilizer of component B.
 12. A compositionaccording to claim 9 comprising a further component selected fromsolvents, pigments, dyes, plasticizers, antioxidants, stabilizers,thixotropic agents, levelling assistants, further light stabilizers,metal passivators, phosphites and phosphonites.
 13. A compositionaccording to claim 12 comprising as further component a light stabilizerfrom the class of the 2-hydroxyphenyltriazines and/or2-hydroxyphenylbenzotriazoles.
 14. A process for stabilizing an organicmaterial against damage by light, oxygen and/or heat, which comprisesadding to or applying to said material a compound of the formula I′ orII according to claim
 5. 15. Compound according to claim 5 of one of theformulae a-t

g. R—NH—(CH₂)₆—N(R)—(CH₂)₆—NH—R with R being

s. R—NH—(CH₂)₆—N(R)—(CH₂)₆—NH—R with R being